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Origin of ferroan alabandite and manganoan


sphalerite from the Tisovec skarn, Slovakia

Article in Neues Jahrbuch für Mineralogie - Abhandlungen · April 2011


DOI: 10.1127/0077-7757/2011/0183

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N. Jb. Miner. Abh. 188/2, 119–134 Article
Published online January 2011

Origin of ferroan alabandite and manganoan sphalerite from


the Tisovec skarn, Slovakia

Vratislav Hurai, Monika Huraiová

With 9 figures and 4 tables

Abstract: Sulphidic skarn in an exo-contact zone between diorite and Triassic carbonates contains the Mn-rich minerals ferroan
alabandite (Mn0.84-0.89Fe0.11–0.16S), manganoferroan sphalerite (Zn0.37–0.76Mn0.01–0..36Fe0.22–0.28S), hübnerite, manganoan magnesiohorn-
blende, and Mn-carbonates. The Mn-content in sphalerite (up to 21.4 wt. %) is the highest ever recorded in hydrothermal settings.
Magnetite and sulphides like galena, pyrite, pyrrhotite, arsenopyrite are also present. Anhydrite is ubiquitous as inclusions in
sulphide minerals and crystals in drusy cavities, postdating hydrothermal Ca-Mn-Fe carbonates. Primary aqueous inclusions with
variable salinity (2.9–44.8 wt. % NaCl eq.) occur in sphalerite and Mn-calcite. The fluid inclusions locally exhibit textural evidence
for heterogeneous entrapment of boiling fluids. Crystallization temperatures of 300–350 °C were obtained from various mineral
geothermometers, δ34S values in coexisting galena and sphalerite, and infrared fluid inclusion microthermometry. The observed
anhydrite-chalcopyrite-magnetite-pyrrhotite-arsenopyrite-alabandite assemblage constrains fO2 and fS2values to –34.5 ± 1.5 and
–12.5 ± 0.5 log units, respectively, at 300 °C and atmospheric pressure. Together with an assemblage of silicate minerals (chlorite,
sericite, K-feldspar, hyalophane) and high-salinity fluids, the calculated oxygen and sulphur fugacities are consistent with an inter-
mediate sulphidation hydrothermal system. The increased δ34S values of the ore-forming fluids, 2–2.5 ‰, result from the disequi-
librium isotopic exchange between mantle-derived H2S and marine sulphate.

Key words: alabandite, manganoan sphalerite, skarn, sulphur isotopes, infrared microthermometry, Western Carpathians

1. Introduction town (Fig. 1) revealed massive sulphide ores with hitherto


unknown Mn-rich mineralization. The sulphide assem-
The ore deposits near Tisovec town in central Slovakia blage includes ferroan alabandite associated with manga-
are an example of ancient mining sites, from where mod- noferroan sphalerite with extremely high Mn content, up
ern analytical data are not available. In spite of preserved to 0.36 apfu. Apart from description of mineral paragene-
remnants of mining activity (smelters, dumps, slag heaps, sis, the present study aims to characterize thermodynamic
adits), as well as local geographic names reminiscent of parameters and origin of the ore-forming fluid, employing
the exploitation of iron and silver ores, only few descrip- mineral thermobarometers, fluid inclusion infrared mi-
tions are available, the latest dated 38 years ago. The crothermometry, thermodynamic modelling and sulphur
oldest written record from the beginning of 17th century isotopes. The obtained data will be compared with other
mentions private lead mining works conveyed to estate skarn occurrences of the Western Carpathians.
ownership. Other documents refer to iron ore exploitation
around 1752, and its decline in 1864 (EISELE 1907), subse-
quent resurgence and final breakup of the mining activity 2. Geological setting and previous works
in 19th century (PAPP 1919). Present knowledge is mainly
based on reconnaissance studies and geological mapping The mining area near Tisovec exhibits complex and still
in the middle of 20th century (ADAM et al. 1956, BACSÓ unresolved geological structure composed of: 1. Variscan
1964). crystalline basement of the Veporic unit (granitoids, bio-
Investigation of dump materials on the eastern slopes titic paragneiss with intercalations of acid metavolcanic
of the Magnetový vrch hill, 5 km northwest of Tisovec rocks), 2. weakly metamorphosed autochthonous sedi-
© 2011 E. Schweizerbart’sche Verlagsbuchhandlung, Stuttgart, Germany www.schweizerbart.de
DOI: 10.1127/0077-7757/2011/0183 0077-7757/2011/0183 $ 4.00
eschweizerbart_xxx
120 V. Hurai and M. Huraiová

Fig. 1. Map of old mining works northwest of Tisovec town (BACSÓ 1964) with simplified geological background: 1 – Neogene andesite,
2 – post-Triassic diorite, 3 – Variscan granite and granodiorite of the Veporic unit, 4 – Mesozoic sediments, mainly carbonates, of the Silica
unit and the Veporic cover sequences, 5 – thrusting planes. Asterisk denotes location of dumps with samples studied (GPS coordinates:
latitude 48° 43′ 8″ N, longitude 19° 53′ 48″ E, altitude 765 meters above sea level). Abbreviations in inset: T – Tatric, V – Veporic, G – Ge-
meric tectonic units.

mentary cover of the Veporic unit (arkose, quartzite), 3. formed along contacts between diorite intrusion and Tri-
Carboniferous-Triassic sediments (phyllite, sandstone, assic marly limestone (Fig. 1). Polymetallic Fe-Pb-Zn
conglomerate, quartzite) of the Gemeric unit, 4. Middle- ores precipitated during a hydrothermal sulphidic stage
Upper Triassic limestones and dolomites as a part of the at a greater distance from the intrusion contact. Evidence
Silica nappe. All these elements are intruded by post-Tri- of pneumatolytic-exhalative processes and contact meta-
assic diorites along E-W oriented faults, and by Badenian somatism are found also at a greater distance from the
volcanic rocks (PÉCSKAY et al. 2006), mainly andesites, skarn deposits as macroscopic needles and aggregates of
along younger NW-SE to N-S trending faults (BACSÓ schorl tourmaline along foliation planes of Carboniferous
1964, VOJTKO 1999). quartzite and arkose.
Iron-bearing accumulations near Tisovec were as- Mineralogical studies carried out on magnetite and
signed to a group of contact-metasomatic skarn deposits garnet–bearing skarns focused on the optical proper-
(ADAM et al. 1956). Magnetite- and garnet-bearing skarns ties and chemical composition of anisotropic garnets

eschweizerbart_xxx
Origin of ferroan alabandite 121

(ŠAMAJOVÁ 1966, 1972). A total of three mineralization following standards were used: albite (Na), wollastonite
stages have been distinguished: 1) rare high-temperature (Si, Ca), orthoclase (K), fayalite (Fe), chalcopyrite (Fe,
anorthite-magnetite predating the main skarn formation Cu and S in sulphides), rhodonite (Mn in silicates), chro-
(ŠAMAJOVÁ 1968), 2) skarn-forming stage with pyroxene, mite (Cr), barite (Ba), synthetic SrTiO3 (Sr), Al2O3 (Al),
garnet, sporadic vesuvianite and wollastonite, postdated MgO (Mg), TiO2 (Ti), Mn, Co, Ni, Ag, Bi, ZnS (Zn), Cd,
by epidote and magnetite, 3) post-skarn carbonate-quartz- BaF2 (F), NaCl (Cl), Sb2S3 (Sb), InSb (In), FeAsS (As).
sulphidic hydrothermal stage with pyrrhotite, sphalerite, Conventional correction (ARMSTRONG 1988) was used for
galena, pyrite, marcasite, chalcopyrite and Mn-Fe carbon- conversion of raw data to wt. % of elements and oxides.
ates. Gangue minerals of the latest stage are represented Fluid inclusions were studied in 90–100 μm thick,
by quartz, chlorite, and calcite, and in places also by zeo- doubly polished wafers using an OLYMPUS BX-51IR
lites (ŠAMAJOVÁ 1965). Main sulphidic minerals (pyrite, microscope equipped with a 1.2 mm Hitachi KP-161 in-
pyrrhotite, chalcopyrite) were characterised by means of frared CCD camera at Comenius University, Bratislava.
X-ray powder diffraction and quantitative optical emis- A LINKAM THMSG-600 freezing-heating stage enabled
sion spectrography (CAMBEL & JARKOVSKÝ 1967, 1969). microthermometric measurements of phase transitions.
Structural state and sulphur isotope composition of pyr- The freezing-heating stage was calibrated using natural
rhotite from the Leopold adit was studied by KANTOR & and synthetic fluid inclusions. Accurracy of IR-microther-
ĎURKOVIČOVÁ (1977). mometric measurements was checked in sphalerite-host-
ed fluid inclusions from another locality, visible in both
VIS and NIR spectral ranges. The accuracy of tempera-
3. Analytical techniques ture measurements was ±0.1 °C in the temperature range
between –100° and +100 °C, and ±0.2 °C at greater tem-
Mineral compositions were measured in polished carbon- peratures.
coated thin sections by WDS analysis using a CAMECA Sulphide grains carefully selected under binocular
SX-100 electron microprobe at the Geological Survey, microscope were powdered in agate mortar, mixed with
Bratislava, at the following analytical conditions: 15 kV CuO and annealed in vacuum at 320 °C for 30 minutes
acceleration voltage for silicates, 20 kV for sulphides, 10– to remove volatile impurities. The evacuated and purified
15 nA sample current for silicates, 20 nA for sulphides, sample was then combusted at 770 °C for 30 minutes.
10–15 s counting times and 5 μm beam diameter. The The liberated SO2 gas was purified in cryogenic traps and

Table 1. Overview of mineral phases identified in the samples studied.


Mineral Composition Intergrowths Mode of occurrence
Apatite Fluorapatite (0.44 apfu Mn, 1.1 wt. % F) Ttn inclusions in Gn
Alabandite Mn0.84-0.89Fe0.11-0.16S (Table 2) Mn-Sp, Po isolated grains, inclusions in Gn,
Amphibole Manganoan magnesiohornblende (LEAKE et al. 1997, Table 3) inclusions in Py
Anglesite PbSO4 product of Gn weathering
Anhydrite CaSO4 Dol, Chl, Ms inclusions in Py, drusy cavities in
carbonate veinlets
Arsenopyrite FeAsS (Table 2) Gn aggregates
Dolomite CaMg(CO3)2 Chl, Ms, Anh inclusions in Py
Galena PbS Po, Mn-Sp aggregates
Hübnerite (Mn0.9Fe0.1)WO4 Gn, Mn-Sp, Py inclusions in Rds
Hyalophane (K0.7Ba0.21Na0.08Fe0.03)Al1.18Si2.8O8 (Table 3) inclusions in Py
Chalcopyrite CuFeS2 Po, Sp aggregates, inclusions in Py and Sp
Chlorite Mg-chlorite (WIEWIÓRA & WEISS 1990, Table 3) Dol, Ms, Anh inclusions in Py
Mn-carbonates Mn-calcite, Mn-siderite, rhodochrosite veinlets
Pyrite FeS2 Fe-Sp, Po metacrystals in Sp-Po matrix
Pyrrhotite Fe0.88-0.91S (Table 2) Sp, Gn aggregates, inclusions in Gn
Sphalerite Zn0.37-0.76Mn0.01-0.36Fe0.22-0.28S (Table 2) Po, Gn, Alb aggregates, inclusions in Gn
Titanite CaTiSiO5 (0.13-0.14 apfu Al, 0.5-1.24 wt. % F) Ap inclusions in Gn
White mica Muscovite s.s. (TISCHENDORF et al. 2007, Table 3) Dol, Anh, Chl inclusions in Py

Abbreviations (WHITNEY & EVANS 2010): Alb – alabandite, Anh – anhydrite, Ap – apatite, Chl – chlorite, Dol – dolomite, Gn – galena, Ms
– muscovite, Po – pyrrhotite, Py – pyrite, Rds – rhodochrosite, Sp – sphalerite, Ttn – titanite.

eschweizerbart_xxx
122 V. Hurai and M. Huraiová

Table 2. Representative electron microprobe analyses (wt. %) of alabandite, arsenopyrite, pyrrhotite and sphalerite.

Anal. # 5/7 5/5 6b 6a 10/1 10/2 4/1 5/1-1 5/8 5/4 5/3 9a
Phase Alb Alb Alb Alb Asp Asp Po Po Po Mn-Sp Mn-Sp Fe-Sp
in Gn in Gn in Gn in Gn in Gn in Gn
Fe 9.02 8.60 10.33 9.44 34.88 34.98 60.37 61.30 60.82 16.33 16.85 13.09
Co 0.06 0.05 0.10 0.08
Mn 53.98 54.02 52.35 53.69 1.20 1.04 0.03 20.21 21.38 0.71
Ag 0.02 < mdl 0.02 0.04 0.04 < mdl
Zn 0.02 < mdl < mdl < mdl < mdl 27.35 26.12 51.67
Cd 0.04 0.03 0.02 0.08 0.02 0.31 0.32 0.30
Sb 0.03 < mdl nd nd 0.03 < mdl < mdl 0.06 < mdl 0.13 0.06
Cu < mdl 0.03 < mdl < mdl < mdl < mdl 0.02 0.02 < mdl < mdl < mdl 0.40
In 0.06 0.04 < mdl 0.02 < mdl 0.12 0.05 0.04
Bi 0.23 0.07
As 43.56 44.32 < mdl 0.08
S 36.72 36.48 36.87 36.81 20.74 20.86 39.26 38.78 38.98 34.79 34.94 33.57
Total 99.89 99.22 99.59 100.05 100.47 101.48 99.85 100.32 99.88 99.29 99.71 99.78
Formula proportions on the basis of 1S-
Fe 0.141 0.135 0.161 0.147 0.966 0.963 0.883 0.908 0.896 0.270 0.277 0.224
Co 0.002 0.001 0.001 0.001
Mn 0.858 0.864 0.829 0.851 0.034 0.029 0.000 0.339 0.357 0.012
Ag 0.000 0.000 0.000 0.000 0.000 0.000
Zn 0.000 0.000 0.000 0.000 0.000 0.386 0.367 0.755
Cd 0.000 0.000 0.000 0.001 0.000 0.003 0.003 0.003
Sb 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000
Cu 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.006
In 0.000 0.000 0.000 0.000 0.001 0.000 0.000
Bi 0.002 0.000
As 0.899 0.909 0.000 0.001
Total 1.001 1.001 0.990 0.999 1.900 0.995 0.885 0.910 0.897 0.999 1.004 1.000

< mdl – less than minimum detection limit

Table 3. Representative electron microprobe analyses of chlorite, muscovite, amphibole and K-feldspar inclusions in pyrite.

Phase Chl Chl Ms Ms Am Am Kfs Kfs Kfs Kfs


dark pale
SiO2 30.66 27.17 51.12 52.25 51.42 50.08 57.10 56.75 63.95 64.48
TiO2 0.09 0.03 0.02 0.01 0.02 0.04
Al2O3 20.50 24.86 33.27 32.59 5.20 4.54 20.35 20.34 18.65 18.27
Cr2O3 0.02 < mdl 0.04 0.03 < mdl 0.01
NiO 0.02 0.05 < mdl < mdl 0.03 0.04
FeO 3.19 6.67 1.28 2.33 9.62 7.70 0.49 0.63 0.68 0.60
MnO 0.30 1.86 0.02 0.04 5.31 4.92
SrO 0.06 0.02 0.06 0.02
BaO 10.32 10.61 0.08 0.70
CaO 0.01 < mdl 0.27 0.47 12.52 14.30 0.05 0.02 0.47 0.08
MgO 32.30 26.57 0.93 1.07 13.70 14.43 0.10 < mdl 0.01 0.15
K2O 0.01 < mdl 8.58 7.82 0.21 0.15 10.89 11.12 14.70 15.01
Na2O < mdl 0.01 0.04 0.06 0.56 0.54 1.03 0.82 0.79 0.42
F < mdl 0.14 0.17
Cl < mdl < mdl
Total 87.10 87.22 95.58 96.66 98.58 96.92 100.39 100.31 100.11 99.74

< mdl – less than minimum detection limit

eschweizerbart_xxx
Origin of ferroan alabandite 123

sealed in breakable glass vial. Measurement of sulfur iso- Mn concentrations in the matrix sphalerite are lower, at-
tope ratios were performed using a FINNIGAN MAT 250 taining 18.8 wt. %. Matrix and inclusion sphalerites show
mass spectrometer at Geological Survey, Bratislava. The uninterrupted transition from ferroan (Zn0.76Fe0.22Mn0.01S)
isotopic ratios were expressed in δ-notation as ‰ differ- to manganoferroan (Zn0.37Mn0.36Fe0.28S) compositions.
ence from the international V-CDT standard. Standard er- Alabandite creates rounded inclusions in galena
ror is within ±0.01 % of the obtained value. (Fig. 2c) and isolated grains associated with galena and
Mn-sphalerite in massive sulphide ores. The galena-host-
ed inclusions are sometimes intergrown with Mn-sphal-
4. Mineral compositions and assemblages erite (Fig. 2 g). Iron contents vary between 6.9 and 10.4
wt. %, without any systematic compositional difference
The sulphide mineralization studied occurs in white-to- between the matrix and the inclusion alabandites.
grey fine-grained marly limestones and marbles. Samples Other sulphide minerals, arsenopyrite (closely associ-
ated with galena) and chalcopyrite are present in minor
collected from dumps are represented by massive ores
amounts. Iron oxides are represented by magnetite, which
dominated by pyrrhotite, sphalerite, and pyrite. List of creates isolated grains in the sulphide matrix. Hematite
identified mineral phases and their representative electron was not observed.
microprobe analyses are in Tables 1–3. Sulphate assemblage consists of anhydrite and an-
Pyrrhotite creates coarse-grained aggregates inter- glesite. Anglesite replaces galena along grain boundaries
grown with sphalerite and galena (Fig. 2a, b) or rounded and it probably originated during supergene alteration
inclusions in galena in association with alabandite and of primary ores. In contrast, anhydrite is primary hydro-
Mn-sphalerite (Fig. 2c). Weak iron deficiency and in- thermal mineral. Irregular anhydrite inclusions are ubiq-
creased Co (0.14 wt. %), As (0.18 wt. %) and Mn (0.17 wt. uitous in pyrite metacrystals, where they are closely as-
%) contents are diagnostic for all pyrrhotite types. X-ray sociated with chlorite and dolomite-muscovite aggregates
powder diffraction of pyrrhotites from the Leopold adit (Fig. 2d). Anhydrite was observed also as the latest min-
and their reflected light images in magnetite suspension eral phase in drusy cavities in Mn-carbonates (Fig. 2h).
(KANTOR & ĎURKOVIČOVÁ 1977) revealed complex domain
texture of the hexagonal pyrrhotite with lamellae and
elongated blebs of monoclinic pyrrhotite. The hexagonal 5. Fluid inclusion microthermometry
pyrrhotite is often replaced by the monoclinic pyrrhotite
along grain boundaries. This type of replacement is dis- Primary fluid inclusions in sphalerite exhibit irregular
to negative crystal shapes. Most frequent are two-phase
cernible also in BSE images of our samples (Figs. 2a, b).
inclusions composed of aqueous solution and a vapour
Massive sulphide ores often contain large pyrite hexa- bubble. Multiphase aqueous inclusions with several trans-
hedrons embedded within fine-grained pyrrhotite-sphal- parent and opaque daughter crystals are less abundant.
erite matrix (Fig. 2d). A large number of inclusions were Essentially gas inclusions devoid of optically discernible
identified in the pyrite: manganoan magnesiohornblende water also occur. Secondary inclusions arranged along
(7.1–7.4 apfu Si, 0.44–0.65 apfu Mn2+, Mg/Mg+Fe2+ = healed fractures are represented only by two-phase aque-
0.7–0.8), galena, anhydrite, Mg-chlorite, dolomite, mus- ous inclusions with consistent volume fraction of vapour
covite, hyalophane, potassium feldspar and titanite. Two phase (5–15 vol. %).
types of Mg-chlorites were distinguished in BSE images Phase changes in multiphase inclusions are illustrated
of composite aggregates: brighter chlorite with 0.47–0.54 in Fig. 3. Low temperature phase transitions in multiphase
Fe2+, 1.38–1.45 AlIV, and 3.82–4.01 Mg apfu, darker chlo- inclusions are unknown, because they failed to freeze out
rite with 0.21–0.25 Fe2+, 1.16–1.26 AlIV, and 4.43–4.55 at any temperature down to –190 °C. Phase transition
Mg apfu (Fig. 2e). sequence on heating above 25 °C is as follows: LVS1S2
Sphalerite is abundant sulphide in massive ores. Black → LVS1 277–303 °C→ LS1 308–380 °C→ L, where LVS1S2
69 –190 °C

isometric grains of sphalerite create coarse-grained aggre- designates aqueous liquid, vapour bubble, solid phase 1
gates intergrown with pyrrhotite (Fig. 2b). Some grains and solid phase 2, respectively. The isotropic transparent
exhibit gradual increase in Mn content toward margins soluble daughter phases probably correspond to sylvite
(Fig. 2f). The Mn-rich sphalerite is obviously associ- (S2) and halite (S1).
ated with galena (Fig. 2f), in which it is also enclosed as Unlike multiphase inclusions, two-phase aqueous in-
rounded inclusions intergrown with alabandite (Fig. 2 g) clusions froze out readily on cooling. Eutectic melting
and closely spatially associated with pyrrhotite (Fig. 2c). was observed between –21 and –49 °C. Temperatures of
Mn-sphalerite from intergrowths with alabandite exhibits ice melting varied between –1.7 and –15 °C. Metastable
extremely high Mn contents, up to 21.4 wt. %, while the hydrohalite melting between 20–28.7 °C was observed in

eschweizerbart_xxx
124 V. Hurai and M. Huraiová

Fig. 2. Back-scattered elec-


tron images of ores in the
Tisovec skarn. a) Galena
(Gn) enclosed in massive
hexagonal pyrrhotite (Po-
hex.) aggregate replaced by
monoclinic pyrrhotite (Po-
mon.) along grain bounda-
ries. b) Equi-granular
pyrrhotite-sphalerite aggre-
gate, with galena inclusions in Fe-sphalerite (Sp) and hexagonal pyrrhotite replaced by monoclinic pyrrhotite along grain boundaries. c)
Rounded alabandite (Alb) and pyrrhotite (Po) inclusions in galena. d) Pyrite crystal in fine-grained sulphide matrix. Numerous solid inclu-
sions in the crystals are galena (bright), anhydrite (grey), and dolomite-muscovite aggregates (dark inhomogeneous specks). e) Anhydrite-
chlorite (Chl) aggregate enclosed in pyrite crystal. f) Zoned sphalerite grain showing gradual change from Mn-poor ferroan sphalerite in
centre to manganoferroan sphalerite at margin. Apparent inhomogeneities of the sphalerite grain are caused by scratched carbon coating.
g) Intergrowth of ferroan alabandite and manganoan sphalerite in galena. h) Drusy cavity in massive sulphidic ore filled with manganoan
calcite (Mn-Cal), manganoan siderite (Mn-Sd) and anhydrite (Anh). Inset shows brightness-contrast-enhanced image documenting oscil-
latory zoning of the Mn-calcite.

eschweizerbart_xxx
Origin of ferroan alabandite 125

Fig. 3. Infrared images of primary fluid inclusions in Fe-sphalerite. a) Two-phase inclusion containing aqueous liquid (L) and vapour (V)
phases. b) Group of multiphase brine inclusions with consistent phase ratios. c-f) Sequence of phase transitions on heating. Abbreviations:
V – vapour bubble, L – aqueous liquid, S1- solid phase, probably halite, S2 – solid phase, probably sylvite.

eschweizerbart_xxx
126 V. Hurai and M. Huraiová

Fig. 4. Correlation of total homogenization temperature with salinity in aqueous inclusions. Halite saturation curve and densities of vapour-
saturated NaCl-H2O solutions are from BODNAR (1983).

some two-phase inclusions with high salt content. Total 6. Sulphur isotopes
homogenization to liquid occurred at 204–306 °C.
Eutectic melting between –21 and –30 °C corresponds A total of 19 sulphide samples have been selected for mass
to stable and metastable eutectic temperatures in the H2O- spectrometric determination of 34S/32S isotope ratios. The
NaCl-KCl system; lower temperatures indicate additional obtained δ34S values range between –1.3 and 0.5 ‰ for
Fe-, Mg- and Ca chlorides (BORISENKO 1977). Total salt galena, at 2.3–2.9 ‰ for sphalerite, 1.5–2.4 ‰ for chalco-
contents varied between 2.9 and 44.8 wt. % NaCl eq. pyrite, 2.4–2.8 ‰ for pyrite, and 2.1–2.7 ‰ for pyrrhotite
Fluid inclusions in carbonates from drusy cavities (Table 4). The sulphur isotope ratios in the investigated
in massive sulphidic ores show slightly different phase pyrrhotites significantly differ from the value of –1.5 ‰
transition temperatures. Eutectic temperatures between obtained for the pyrrhotite from the Leopold adit by KAN-
–44 and –56 °C are indicative of aqueous chloride so- TOR & ĎURKOVIČOVÁ (1977).
lutions with divalent cations, mainly CaCl2. The CaCl2
weight fractions estimated from dissolution temperatures
of ice and hydrohalite (VANKO et al. 1988) are 0.37–0.56
of total salt content, which varies between 3 and 43 wt. Table 4. Sulphur isotope composition of sulphides (‰ V-CDT).
% NaCl eq. Increased CO2 concentrations in some car-
bonate-hosted, halite-containing inclusions are indicated Sample Py Gn Sp Cp Po T (°C)*
by the nucleation of CO2-clathrate on cooling and sub- T1/10b –1.28 2.61 143–173
sequent dissolution at warming to around –5 °C. CO2- T1/1a 2.66 2.71 2.4 2.71
liquid phase was not observed. Total homogenization T1/2 2.41 2.09
temperatures, either by vapour bubble disappearance or T1/6 0.47 2.87 256–295
T1/18 2.72 2.86 1.5 2.31
halite dissolution, are comparable with those in sphaler-
T1/24 2.83 1.7 2.13
ite, but a number of Th values are shifted below 200 °C, T0H-1 0.11 2.27 285–326
thus indicating a lower trapping temperature (Fig. 4). No
correlation exists between salinity and total homogeniza- * temperatures calculated assuming equilibrium isotope fractiona-
tion temperature for the inclusions trapped in sphalerite tion between coexisting galena and sphalerite (OHMOTO & RYE
and calcite. 1979)

eschweizerbart_xxx
Origin of ferroan alabandite 127

Fig. 5. Phase diagram of the Fe-S and Fe-As-S systems at atmospheric pressure compiled from TOULMIN & BARTON (1964), KRETSCHMAR &
SCOTT (1976), OSADCHII & CHAREEV (2006). Dashed lines are isopleths for atomic % of As in arsenopyrite (Asp), thin solid lines are isople-
ths of mol. % FeS in pyrrhotite in the Fe-S system (TOULMIN & BARTON 1964), thick solid lines are phase boundaries. Other abbreviations:
Po – pyrrhotite, Py – pyrite, Lö – löllingite, Fe – native iron, As – native arsenic, L – liquid.

7. Interpretations an episodic trapping of halite-oversaturated brines cannot


be ruled out, though a similar trend can be explained by
7.1. Homogenization temperatures of fluid dilution of homogenous high-salinity brines. We did not
inclusions find evidence for the entrapment of halite-oversaturated
brines in the form of halite-dominated inclusions. Moreo-
Gas inclusions and variable water volume fractions in a ver, the polyphase inclusions normally exhibit rather con-
group of coeval inclusions yield evidence for episodic sistent homogenisation and dissolution temperatures, and
boiling of sphalerite- precipitating fluid. In view of this therewith not favouring the concept of heterogeneous L+H
observation, minimum total homogenization tempera- trapping. Anyway, homogenization in polyphase brine in-
tures of liquid-rich inclusions are likely to approximate clusions homogenizing by halite dissolution, 277–303 °C,
the mineral crystallization temperature. provides the most reliable estimate of the minimum crys-
Polyphase inclusions often homogenize by halite dis- tallisation temperature. Except for an outlier at 209 °C,
solution, and this behaviour is diagnostic of either homo- total homogenization temperatures of two-phase primary
geneous trapping at a higher pressure, or heterogeneous inclusions are also rather consistent (234–306 °C), and
trapping of halite-oversaturated brine. In the first case, the these can also be considered with a great deal of certainty
temperature of total homogenization represents the lower- as minimum possible, pressure-uncorrected trapping tem-
most temperature of crystallisation. In the second case, the peratures. On the other hand, the maximum temperature
lowermost limit is defined by the homogenization temper- of halite dissolution (380 °C) can be considered as the up-
ature of the bubble in the presence of halite. Due to wide per temperature limit for the sphalerite crystallisation in
range of the halite dissolution temperatures (158–380 °C), the case of episodic halite oversaturation of the ore fluids.

eschweizerbart_xxx
128 V. Hurai and M. Huraiová

Fig. 6. Sulphur isotope ratios in coexisting galena and sphalerite projected on temperatures and δ34S values of the equilibrium H2S gas
(OHMOTO & RYE 1979).

In case of homogeneous trapping, the maximum tempera- blage at temperatures between 300–500 °C (BOORMAN
ture may be higher. In conclusion, the microthermometric 1967), but it is within the limit of 19–23 mol. % as sug-
data place the most probable crystallisation temperature gested by LEPETIT et al. (2003). Pyrite sometimes replaces
of sphalerite to the range of 234–306 °C. pyrrhotite along grain boundaries, and pyrite has not been
observed as inclusions in galena. Hence, we assume that
most ferroan sphalerite coexisted only with pyrrhotite at
7.2. Pyrrhotite-arsenopyrite ± pyrite equilibria low temperature and low sulphur fugacity.
Similarly arsenopyrite, which is closely associated
Pyrrhotite-pyrite equilibrium allows the estimation of with galena, provides information about the crystallisa-
temperature and sulphur fugacity (TOULMIN & BARTON tion temperature of accompanied alabandite, Mn-sphaler-
1964, OSADCHII & CHAREEV 2006) in sub-volcanic envi- ite and pyrrhotite. Arsenic contents between 31.0 and 31.3
ronments, where pressure plays an insignificant role. The at. % correspond to temperatures of 362–383 °C, and sul-
range of FeS contents in pyrrhotite (93.4–95 mol. %) from phur fugacities between –7.6 and –8.2 log units, assum-
the Tisovec skarn corresponds to a wide range of tempera- ing equilibrium with pyrrhotite and pyrite (KRETSCHMAR
tures, 250–467 °C, and sulphur fugacities, between –5 and & SCOTT 1976). These temperatures must be considered
–13.5 log units (Fig. 5). Maximum FeS content in ferroan as uppermost limits as pyrite is absent in this mineral as-
sphalerite, 22.3 mol. %, is by 1 mol. % higher than that semblage. On the other hand, the lowermost temperature
in the sphalerite buffered by the pyrite-pyrrhotite assem- and sulphur fugacity, 282–307 °C and –12.3 to –13.5

eschweizerbart_xxx
Origin of ferroan alabandite 129

Fig. 7. Summary of T-fS2 parameters constrained by fluid inclusions, mineral thermo-barometers and sulphur isotopes.

logfS2 units, are constrained by the absence of löllingite. and δ34SH2S values range at 143–326 °C and 2.0–2.5 ‰,
Assuming equilibrium conditions between arsenopyrite respectively (Fig. 6).
and pyrrhotite, the isopleths for the minimum As content
in arsenopyrite (31 at. %) and the maximum FeS content
in pyrrhotite (95 mol. %) intersect at ~325 °C and –10.5 7.5. Thermodynamic model
logfS2. However, about 30 % of the pyrrhotites, with less
than 94.2 mol. % FeS, is out of equilibrium with the ob- T-fS2 parameters constrained by fluid inclusions and min-
served arsenopyrite composition. eral equilibria are summarized in Fig. 7. Temperatures be-
tween 300 and 325 °C, representing the intersection of all
geothermometers, are considered to be the best estimate
7.3. Chlorite thermometer for the alabandite-sphalerite-pyrrhotite assemblage.
The temperature of 300 °C was used as input for ther-
The chlorite thermometer (CATHELINEAU 1988) applied to modynamic modelling with the aim to calculate oxygen
zoned aggregates of chlorite associated with anhydrite fugacity (Fig. 8). The latter parameter controls the ratio of
enclosed in pyrite crystals (Fig. 2d-e) yields temperatures oxidised and reduced sulphur, and is therefore needed to
from 366 °C to 382 °C for Fe-rich chlorites and 297– evaluate the reliability of δ34Sfluid values and temperatures
330 °C for Mg-rich chlorite. The inferred temperatures, inferred from sulphur isotope ratios in coexisting galena
however, not necessarily represent the crystallisation con-
and sphalerite.
ditions of alabandite and sphalerite, because these miner-
Thermodynamic modelling was made at a reference
als are not associated with chlorites in the assemblage of
pressure of 1 bar in order to allow correlation with ex-
the pyrite-hosted inclusions.
perimental sulphide systems. Oxygen and sulphur chemi-
cal potentials were calculated by using the PERPLE_X
7.4. Sulphur isotopes ’06 computing package (CONNOLLY 1990) and database of
minerals, gases and gaseous species included in the SUP-
Galena is most depleted and sphalerite is most enriched in CRT92 program (JOHNSON et al. 1992). The hard sphere-
34
S. This is in accord with equilibrium isotope fractiona- modified Redlich-Kwong equation of state involved in the
tion in the sulphide-H2S system (OHMOTO & RYE 1979). computing package was employed for the calculation of
As both minerals must have crystallised simultaneously the equilibrium H-O-S fluid composition.
(Fig. 2a, b) we may use their sulphur isotope compositions Limits of oxygen and sulphur fugacities are con-
for calculating the formation temperature and the δ34S strained by the presence of chalcopyrite in the stability
value of the parental fluid. The calculated temperatures field of anhydrite, and the absence of hematite. The up-

eschweizerbart_xxx
130 V. Hurai and M. Huraiová

Fig. 8. Schreinemaker’s phase diagram for the Fe-Cu-S-O system at 300 °C and 1 bar, with selected univariant curves from the Ca-S-O,
Mn-S-O and Pb-S-O systems calculated using PERPLE_X ’06 package. Contoured are stability fields of alabandite (Alb), anglesite (Ang),
anhydrite (Anh), bornite (Bn), covellite (Cv), chalcocite (Cc), chalcopyrite (Ccp), galena (Gn), hematite (Hem), lime - CaO, magnetite
(Mag), manganosite (Mng), pyrite (Py), pyrrhotite (Po), position of a quartz-fayalite-magnetite buffer (αQFM), and H2S/SO2 ratios in
the equilibrium gas, and invariant points: 1) Mag-Po-Bn-Ccp, 2) Mag-Po-Py-Ccp, 3) Mag-Hem-Bn-Cc, 4) Mag-Hem-Bn-Ccp, 5) Mag-
Hem-Py-Ccp, 6) Hem-Py-Bn-Ccp. The black trapezoid overlaps the most plausible range of fO2-fS2 parameters inferred from the mineral
assemblage of the Tisovec skarn.

permost log fS2 limit of –11.5 is defined by the pyrrhotite- rium conditions, the sulpho-carbonic gas is reduced, and
pyrite equilibrium. However, because pyrite replaces pyr- dominated by CH4 and H2S, with H2S contents exceeding
rhotite along grain boundaries, it is reasonable to assume that of SO2 by at least ten orders of magnitude.
that ferroan alabandite and manganoferroan sphalerite
crystallised within the stability field of pyrrhotite, and the
corresponding sulphur fugacities are more accurately re- 8. Discussion
flected by the arsenopyrite composition. In summary, the
anhydrite-magnetite-chalcopyrite-pyrrhotite-arsenopy- Mn-enrichment, the presence of K-feldspar-sericite and
rite-alabandite assemblage and the absence of bournonite pyrite-chlorite assemblages, mixed low-to-high-salinity
brackets the fO2 values in the system to the range from aqueous fluids and relatively high formation temperatures
–33 to –36 log units, and those of fS2 to –12.5 ± 0.5 log are similar to adularia-sericite-type base metal sub-vol-
units. At 300 °C, these conditions must have been slightly canic deposits (HEALD et al. 1987). Such deposits form in
below the Mag-Po-Py-Ccp invariant point (2). At equilib- geothermal systems, where meteoric water may mix with

eschweizerbart_xxx
Origin of ferroan alabandite 131

Fig. 9. Compositional variations of alabandite and


sphalerite in the Tisovec skarn

deep, hot, saline, and nearly neutral-pH magmatic waters the initial δ34Sfluid value at Tisovec could be close to 0 ‰,
at depth. In contrast to high sulphidation, acidic-sulphate- thus being diagnostic of a mantle-derived source. The ob-
type deposits formed in root zones of volcanic domes, the served final 34S enrichment of the parental fluid, between
adularia-sericite-type is not directly associated with in- 2 and 2.5 ‰, can be attributed to sulphate-sulphide iso-
trusive volcanism (ibid.). According to the assemblage of topic exchange disequilibrium during simple adiabatic
sulphide minerals, high Fe-content in sphalerite, and the mixing reactions.
calculated sulphur and oxygen fugacities, the sulphidic High salinity fluids and essentially mantle isotopic sig-
carbonate-replacement skarn near Tisovec can be classi- nature of sulphur modified by marine sulphate document-
fied as a medium-sulphidation sub-volcanic system. ed in the Tisovec skarn were for the first time recognized
Thermodynamic parameters and sulphur isotopes at in the Western Carpathian sub-volcanic settings. Retro-
Tisovec indicate strongly reduced parental fluid, which grade calcite, quartz and sphalerite in genetically similar
was significantly enriched in 34S compared to the mantle- skarn deposit at Vyhne-Klokoč in central volcanic zone
derived reservoir with the δ34S value close to zero. The of the Neogene Štiavnica stratovolcano (~85 km SWW
inferred δ34S values in Tisovec sulphidic ores are higher of Tisovec) trapped only diluted (0–4 wt. % NaCl eq., Th
than those in typical magmatic hydrothermal deposits = 215–380 °C) aqueous solutions with signs of boiling,
(porphyry-copper deposits and skarns) with δ34S in sul- while high-salinity aqueous inclusions (up to 22.8 wt.
phides between –3 and +1 ‰ (HOEFS 2009). Such enrich- %) attributed to magmatic fluid were found only in early
ment probably reflects an isotopic exchange with marine garnet (KODĚRA et al. 1998). Mixing of fluids of different
sulphate probably originating from evaporites. origins (magmatic vs. present-day meteoric water) was
Examination of chemical reactions in seafloor hydro- indicated by oxygen and hydrogen isotope ratios in OH-
thermal systems has shown that adiabatic mixing at tem- bearing skarn minerals and fluid inclusions (KODĚRA et al.
peratures around 350 °C can produce δ34S values between 2004).
1.5 and 4.5 ‰ during the precipitation of sulphides. The Occurrence of Mn-bearing minerals (ferroan alaban-
δ34S of the solution increases only if the chemical equilib- dite, manganoferroan sphalerite, hübnerite) in the Tis-
ria are coupled with sulphate-sulphide isotopic exchange ovec skarn merits some special comment. Alabandite has
disequilibrium. In such case, the maximum increase cor- been described from a variety of geological settings of
responds to 2 ‰ above the initial δ34Sfluid value due to the the Western Carpathians: 1. metamorphosed stratiform
limited reducing capacity of the hydrothermal solution pre-Variscan volcanic-exhalative pyrite-pyrrhotite and
(JANECKY & SHANKS 1988). In accord with this model, Mn-carbonate deposits, 2. Early-Cretaceous siderite-

eschweizerbart_xxx
132 V. Hurai and M. Huraiová

polymetallic and quartz-stibnite veins in low-grade Palae- or domains with variable Mn contents have not been ob-
ozoic basement, 3. polymetallic veins and porphyry-type served. Alabandite-sphalerite intergrowths exhibit fuzzy
disseminated mineralizations in central zones of Miocene boundaries (Fig. 2 g). However, electron microprobe
stratovolcanoes (KODĚRA et al. 1990). From genetic point analyses confirm distinct immiscibility gap in the hypo-
of view, the Western Carpathian occurrences of alaban- thetic (MnFe)S-(Zn,Fe)S solid solution, due to negligibly
dite are similar to those known worldwide (OLIVO & GIBBS low ZnS content, few thousandths of mole fractions, in
2003, TRACY & BEARD 2003, and references therein). the coexistent alabandite (Fig. 9). The observed composi-
However, except for the alabandite from metamorphosed tional variation agrees with experimental studies, showing
pyrite-pyrrhotite ores (KANTOR & KRIŠTÍN 1973), other ~ 50 mole % MnS in wurtzite, and essentially no ZnS
Western Carpathian occurrences are poorly documented. substitution in MnS (KANEKO et al. 1984). It is likely that
Descriptions of alabandite dating from 19th century have the gradually increasing Mn contents in zoned sphalerite
not been confirmed recently. The only recent identifica- from Tisovec (Fig. 2f) are accommodated by the change
tion of alabandite by means of electron microprobe comes of galena-type to wurtzite-type lattice.
from an Au-bearing quartz-polymetallic vein genetically The manganoferroan sphalerite from Tisovec contains
linked with a Miocene quartz-porphyry intrusion in the the highest Mn concentration recorded so far in hydro-
central horst structure of the Štiavnica stratovolcano of thermal settings. Available literature sources report on
Central Slovakia (FERENC et al. 2009). Mn-rich sphalerite with 0.25 Mn apfu associated with
Strong iron and manganese enrichment is typical of alabandite in epithermal Ag-bearing sub-volcanic deposit
sphalerites from the Tisovec skarn. FeS content in sphal- at Santo Toribio, Peru (OLIVO & GIBBS 2003), alabandite-
erite is controlled by the activity of FeS in the coexist- hosted sphalerite inclusions with up to 13.4 wt. % Mn in
ing iron sulphides. The sphalerite solvus reaches the FeS Neogene sub-volcanic epithermal Au-Te veins at Sac-
maximum of 19–23 mol. % in the presence of pyrite and arîmb, Romania (CIOBANU et al. 2005), and an average
pyrrhotite and 51–53 mol. % along the iron-troillite buffer Mn content of 9.9 wt. % in Cu-Ag-In-Sn-rich sphalerite
(BOORMAN 1967, LEPETIT et al. 2003). Significant amounts from Cretaceous granite-related sulphide-manganese (al-
of ferric iron can be present if sphalerites contain more abandite-rich) veins in the Vysokogornye ore field, Russia
than 6 mol. % FeS (LEPETIT et al. 2003). FeS contents in (KOKIN et al. 2010). Compositions of sphalerite and the as-
ferroan sphalerite from Tisovec (19–22 mol. %) are close sociated alabandite from the Tisovec skarn overlap those
to the maximum limit defined by the pyrite-pyrrhotite described from the Oldoinyo Lengai natrocarbonatites
buffer, but they increase up to 28 mol. % in the manga- (Tanzania), where both minerals crystallized as primary
noferroan sphalerite (Fig. 9). Substantial Fe3+ contents are magmatic phases at temperatures over 650 °C (MITCHELL
unlikely to be present, as electron microprobe analyses & BELTON 2004).
with total iron expressed as Fe2+ sum around 100 % (Ta-
ble 2). The sphalerite compositions, however, differ from
those in the adularia-sericite-type base metal deposits, Acknowledgements
where FeS contents vary typically between 1 and 4 mol.
% (HEALD et al. 1987). Financial support was provided by the Ministry of Envi-
Increased manganese contents are common in natural ronment and the Geological Survey of Slovakia project
sphalerites associated with Mn-rich minerals (COOK et al. No. 0503, and the grant No. 2/0040/08 from the VEGA
2009). Manganese incorporation in sphalerite takes place agency. Thanks are due to V. HARČOVÁ and P. ČECH for
by simple cationic exchange: Zn2+ ↔ Mn2+. However, the mass spectrometric and to P. KONEČNÝ for electron mi-
galena-type sphalerite structure can adopt only 7 mol. croprobe analyses. Early draft of the manuscript greatly
% MnS as solid solution (SOMBUTHAWEE at al. 1978). In benefited from constructive comments of C. CIOBANU
contrast, the hexagonal wurtzite absorbs approximately (Adelaide) and an anonymous reviewer.
50 mol. % MnS. The extent of the Zn-Mn substitution
is temperature-independent (KANEKO et al. 1984). Larger
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Received: June 11, 2010; accepted: July 30, 2010.


Responsible editor: R. Klemd

Authors’ address:
VRATISLAV HURAI, Geological Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 840 05 Bratislava, Slovak Republic;
vratislav.hurai@savba.sk
MONIKA HURAIOVÁ, Department of Mineralogy and Petrology, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovak Republic;
huraiova@fns.uniba.sk

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